EP2221324B1 - Verfahren zur Herstellung von verbesserten aliphatischen Dicarboxylsäure-Copolymeren - Google Patents

Verfahren zur Herstellung von verbesserten aliphatischen Dicarboxylsäure-Copolymeren Download PDF

Info

Publication number
EP2221324B1
EP2221324B1 EP10152291A EP10152291A EP2221324B1 EP 2221324 B1 EP2221324 B1 EP 2221324B1 EP 10152291 A EP10152291 A EP 10152291A EP 10152291 A EP10152291 A EP 10152291A EP 2221324 B1 EP2221324 B1 EP 2221324B1
Authority
EP
European Patent Office
Prior art keywords
acid
grams
dicarboxylic acid
initiator
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP10152291A
Other languages
English (en)
French (fr)
Other versions
EP2221324A1 (de
Inventor
Marianne P. Creamer
Joseph Manna
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rohm and Haas Co
Original Assignee
Rohm and Haas Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rohm and Haas Co filed Critical Rohm and Haas Co
Publication of EP2221324A1 publication Critical patent/EP2221324A1/de
Application granted granted Critical
Publication of EP2221324B1 publication Critical patent/EP2221324B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]

Definitions

  • the present invention relates to the production of aqueous solutions or dispersions of high molecular weight, high solids copolymers of aliphatic dicarboxylic acids, especially maleic acid, with ⁇ , ⁇ -ethylenically unsaturated monomers having carboxyl or sulfonic acid groups, such as (meth)acrylic acid or 2-acrylamido-2-methyl propane sulfonic acid (AMPS), respectively, which solutions or dispersions have a very low residual content of unpolymerized dicarboxylic acid monomer.
  • Such copolymers are useful as antiscalants, dispersants, detergent additives, deflocculants and fluid retention aids for water-based drilling fluids used in oil drilling operations.
  • Copolymers of aliphatic monoethylenically unsaturated mono-and dicarboxylic acids are well known and have been used as incrustation inhibitors and deflocculants in aqueous systems, and as builders in detergent compositions. Such copolymers have been prepared by copolymerizing a monoethylenically unsaturated aliphatic dicarboxylic acid, such as maleic acid, with one or more monoethylenically unsaturated monocarboxylic acids, and/or monoethylenically unsaturated sulfonic acids. Examples of monocarboxylic acid monomers are acrylic and methacrylic acid. These acid monomers are collectively referred to in the specification and appended claims as "(meth)acrylic acid".
  • EP-A-0663408 and EP-A-0441022 disclose processes for preparation of low molecular weight polymers of monoethylenically unsaturated dicarboxylic acids.
  • the present invention solves the problems of the art by providing a process whereby a single charge neutralization of the reaction mixture is employed at the start of the polymerization reaction along with running the reaction mixture at high solids.
  • This combination has been found to produce high molecular weight polymers having low residuals that also contain high end of feed solids. This combination is particularly useful in providing improved binding of laundry granules thereby preventing dusting.
  • high molecular weight or “increased molecular weight” is meant a weight average molecular weight greater than 70,000 up to 180,000 daltons.
  • high solids or “high solids content” is meant calculated or measured percent solids (ie non-volatile material charged to the reaction vessel), at the end of monomer feeds to the reaction vessel.
  • residuals is meant the total amount by weight of unreacted dicarboxylic acid divided by the total weight of the reaction mixture expressed in parts per million.
  • ppm is parts per million based upon total weight of the subj ect material.
  • an aqueous solution of at least one monoalkali metal or monoammonium salt of a dicarboxylic acid monomer is placed in a suitable reactor and one or more water soluble salts of transition metal ions, generally as aqueous solutions, are added thereto.
  • Suitable monoethylenically unsaturated aliphatic dicarboxylic acids used in the present process contain from 4 to 6 carbon atoms, examples of which are maleic acid, itaconic acid, mesaconic acid, fumaric acid, methylene malonic acid, citraconic acid and their monoalkali metal or monoammonium salts. Depending upon the geometrical location of the carboxyl groups (cis position), they may be added to the aqueous solvent system in the form of their anhydrides, maleic anhydride being typical of such anhydrides.
  • the dicarboxylic acid monomer will generally comprise from 10 to 50 percent, alternatively 35 to 45 percent, by weight of total monomers.
  • Suitable ⁇ , ⁇ -ethylenically unsaturated monomers which are copolymerized with the dicarboxylic acid monomers according to the process of this invention are of three particular types, namely, (a) aliphatic monocarboxylic acids having 3 to 10 carbon atoms and the alkali metal and/or ammonium salts of such acids; (b) organic sulfonic acid compounds and the alkali metal and/or ammonium salts thereof, and (c) vinyl monomers free of carboxyl and sulfonic acid groups, and mixtures of such (a), (b) and (c) monomers.
  • the (a), (b) and (c) monomers comprise from 50 to 90 percent, alternatively from 55 to 65 percent, of said copolymers, based on the total weight of monomers. However, for solubility reasons, some of the (c) monomers do not comprise more than 30 percent of the total monomers, the remainder of the monomers being either the dicarboxylic acid or a mixture of dicarboxylic acid and (a) and/or (b) type monomers in the above-stated proportions.
  • the (a) type monomers include but are not limited to, acrylic and lower alkyl substituted acrylic acid such as methacrylic acid, acrylic and methacrylic acid being referred to collectively herein as "(meth)acrylic” acid, vinyl acetic acid, and the alkali metal, e.g. sodium and potassium, and ammonium salts of such monocarboxylic acids.
  • the (b) type monomers include, but are not limited to, allylsulphonic acid, methallylsulphonic acid, sulfonic acid monomers, such as vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrene sulfonic acid, vinyltoluenesulfonic acid, acrylamido alkyl sulfonic acid, and the alkali metal and ammonium salts of such sulfonic acids.
  • allylsulphonic acid such as vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrene sulfonic acid, vinyltoluenesulfonic acid, acrylamido alkyl sulfonic acid, and the alkali metal and ammonium salts of such sulfonic acids.
  • the acrylamido alkyl sulfonic acid monomers can be prepared by well-known processes which are described in U. S. Pat. No. 3,506,707 and the patents referred to therein.
  • the monomer which has been found to be particularly suitable for use in the process of this invention is 2-acrylamido-2-methylpropane sulfonic acid, or a salt thereof, commonly referred to as "AMPS".
  • the third type monomer copolymerizable with the dicarboxylic acid monomer, and monomer types (a) and (b) if also present, are the vinyl monomers (c), which are free of carboxyl and sulfonic acid groups.
  • Typical of such monomers include but are not limited to ethyl acrylate, tert-butyl acrylamide, vinyl acetate, allyl alcohol, acrylamide, N, N' 1-dimethylacrylamide, N-methylolacrylamide, N,N' 1-methylenebisacrylamide, vinyl crotonate, ethylene glycol diacrylate, tripropylene glycol diacrylate, diallyl dimethyl ammonium chloride, diallylphthalate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, vinyl pyrrolidone and N-vinyl-N-methylacetamide.
  • some of the type of the type include but are not limited to ethyl
  • Suitable transition metal ions used in the process may be selected from the group consisting of Zn 2+ , Co 3+ , Co 2+ , Cu 2+ , Mo 2+ , Fe 3+ , Fe 2+ , Cr 3+ , Ni 2+ , Ce 4+ and Ce 2+ . Mixtures of such ions may also be used.
  • the concentration of transition metal ions in the aqueous solvent system should be a small amount effective to reduce the residual content of the residual unpolymerized monoethylenically unsaturated dicarboxylic acid in the aqueous copolymer solution so as not to exceed 5000 ppm, by weight of dried polymers produced in the polymerization process.
  • the transition metal ion concentration may vary from 0.5 to 100 ppm, based on the total aqueous polymerization system, including monomers and initiator. Alternatively, the transition metal ions are present at a concentration of from 0.5 to 10 ppm.
  • the transition metal ions may be added to the aqueous solvent system in the form of their salts and oxides which are soluble in aqueous solvent system.
  • Suitable water soluble salts include zinc nitrate, zinc sulfate, zinc chloride, cupric acetate, cupric chloride, molybdenous chloride, cobalt (II) acetate, cobalt (II) nitrate, cobalt (III) chloride, ferric chloride, ferric sulfate, ferrous sulfate, chromium (II) acetate, chromium (II) chloride, nickel (II) sulfate, cerium (IV) sulfate, and cerium (II) nitrate.
  • these salts are added to the aqueous solvent system in the form of an aqueous solution of the desired concentration.
  • Aqueous solutions of one or more of the (a), (b) and (c) monomers and water soluble, radical generating initiator are typically co-fed to the reaction vessel over a period of less than or equal to three hours, e.g. 2 to 3 hours or alternatively 1.5 to 2 hours.
  • the aqueous solvent system containing the monomers and initiator is maintained at a temperature of from 40° to 150° C, alternatively 80° C to 100° C. If the temperature of the reaction mixture exceeds the boiling point thereof, the reaction may be carried out under pressure.
  • An alkaline substance is charged to the system at the start of the polymerization reaction to neutralize the dicarboxylate mixture.
  • Suitable alkaline substance include but are not limited to alkaline metal hydroxides, such as sodium hydroxide and potassium hydroxide; sodium carbonate, potassium carbonate, or lithium carbonate; ammonia; calcium hydroxide, magnesium hydroxide, or cesium hydroxide; and organic amines, such as monoethanolamine. These may be used either alone respectively or in combinations with each other.
  • alkaline metal hydroxides such as sodium hydroxide and potassium hydroxide
  • sodium carbonate, potassium carbonate, or lithium carbonate such as sodium carbonate, potassium carbonate, or lithium carbonate
  • ammonia calcium hydroxide, magnesium hydroxide, or cesium hydroxide
  • organic amines such as monoethanolamine.
  • the alkaline substance is charged in a mole amount relative to the amount of monoethylenically unsatured dicarboxylic acid (or anhydride) monomer(s). Such mole ratios range from 2.2:1 to 1.7:1 or alternatively from 2:1 to 1.8:1 of the alkaline substance (caustic) to the dicarboxylic acid monomer.
  • the pH at the start of the monomer and initiator feed ranges from 9.5 to 7.5 or alternatively from 8 to 8.5.
  • the pH at the completion of the monomer and initiator feed ranges from 4 to 5.5 or alternatively from 4 to 5.
  • Suitable water soluble, radical generating initiator are well known and generally include without limitation peroxides such as hydrogen peroxide, hydroperoxides such as t-butylhydroperoxide, and persulfates such as sodium, potassium and ammonium persulfate.
  • peroxides such as hydrogen peroxide
  • hydroperoxides such as t-butylhydroperoxide
  • persulfates such as sodium, potassium and ammonium persulfate.
  • Water-soluble azo initiators such as 2,2.' 1-azobis(2-amidinopropane)hydrochloride can also be used. These initiators can be used alone or in combination.
  • a particularly effective initiator is hydrogen peroxide alone or in combination with sodium persulfate.
  • the total amount of initiator(s) employed generally will be from 0.5 to 5 percent or alternatively from 1-3 percent, by weight of total monomers.
  • a redox system can be used where lower polymerization temperatures are used. Using a redox system requires purging of the aqueous solution(s) of monomers with an inert gas, such as nitrogen. Suitable reducing agents are ascorbic acid and erythorbic acid.
  • GPC gel permeation chromatography
  • Gel permeation chromatography otherwise known as size exclusion chromatography, actually separates the members of a distribution of polymer chains according to their hydrodynamic size in solution rather than their molar mass. The system is then calibrated with standards of known molecular weight and composition to correlate elution time with molecular weight.
  • GPC gel permeation chromatography
  • the process is carried out in the absence of organic chain transfer agents, such as isopropanol, which limit the solids content of aqueous solutions of the copolymers to 25 percent and result in high percentages of unreacted dicarboxylic acid monomer.
  • organic chain transfer agents such as isopropanol
  • the free carboxyl groups on the copolymer can be neutralized by addition of a suitable base, such as sodium hydroxide.
  • the copolymers obtained according to the process of this invention will have a weight average molecular weight of from 70,000 to 180,000 daltons.
  • Example #1 (Weight % Composition: 55 % Acrylic Acid /45% Maleic Acid)
  • An initiator solution of 2.1 grams of sodium persulfate dissolved in 20 grams of deionized water was mixed and 11.41 grams of 35% hydrogen peroxide was added to the sodium persulfate solution, mixed well and added to a syringe for addition to the kettle.
  • a monomer pre-charge solution of 21.04 (0.291 moles) grams of glacial Acrylic Acid was placed in a vial and set aside.
  • An initiator pre-charge solution was prepared by dissolving 1.48 grams of sodium persulfate dissolved in 8 grams of deionized water and adding 3.66 grams of 35% hydrogen peroxide, and set aside.
  • a promoter solution of 4.5 grams of a 0.15% iron sulfate heptahydrate solution was added to a vial and set aside.
  • the promoter solution was added, followed by the acrylic acid pre-charge. After 1 minute, the initiator pre-charge solution was added to the kettle. The expected exotherm of 2 - 5 °C was observed within 5 minutes. One minute after peak exotherm, the monomer and initiator cofeeds began and added linearly and separately over 120 minutes at 91-93°C. At the completion of the feeds, 12 grams and 4 grams of deionized water were added to the monomer and initiator feed vessels, respectively as rinses. The reaction was held for 20 minutes at 91°C. The end of feed theoretical solids was 51.2%. (The measured end of feeds solids was 52.2%).
  • a chase promoter solution of 4.5 grams of a 0.15% iron sulfate heptahydrate solution and 80 grams of deionized water was mixed and set aside.
  • the chaser solution of 0.5 grams of sodium persulfate dissolved in 5 grams of deionized water and adding 1.42 grams of 35% hydrogen peroxide, and set aside.
  • the promoter solution was added to the kettle and the persulfate / peroxide solution was added to the kettle over 5 minutes. The reaction was then held for another 30 minutes.
  • the following solution was prepared: a scavenger solution of 11.4 grams of sodium metabisulfite dissolved in 32 grams of deionized water.
  • Example #1 was repeated, with the following difference: Deionized water kettle charge was 331 grams, which yielded a theoretical end of feed solid of 46.8%. (The measured end of feeds solids was 49.15%).
  • Example #2 (Weight % Composition: 55 % Acrylic Acid /45% Maleic Acid)
  • Example #1 was repeated, with the following differences: Deionized water kettle charge was 188 grams, which yielded a theoretical end of feed solid was 53.1%. (The measured end of feeds solids was 52.7%).
  • Example #3 (Weight % Composition: 60% Acrylic Acid /40% Maleic Acid)
  • An initiator solution of 2.1 grams of sodium persulfate dissolved in 20 grams of deionized water was mixed and 16.94 grams of 35% hydrogen peroxide was added to the sodium persulfate solution, mixed well and added to a syringe for addition to the kettle.
  • a monomer pre-charge solution of 22.81 (0.316 moles) grams of glacial Acrylic Acid was placed in a vial and set aside.
  • An initiator pre-charge solution was prepared by dissolving 1.48 grams of sodium persulfate dissolved in 8 grams of deionized water and adding 7.33 grams of 35% hydrogen peroxide, and set aside.
  • a promoter solution of 4.5 grams of a 0.15% iron sulfate heptahydrate solution was added to a vial and set aside.
  • the promoter solution was added, followed by the acrylic acid pre-charge. After 1 minute, the initiator pre-charge solution was added to the kettle. The expected exotherm of 2 - 5 °C was observed within 5 minutes. One minute after peak exotherm, the monomer and initiator cofeeds began and added linearly and separately over 120 minutes at 91-93°C. At the completion of the feeds, 12 grams and 4 grams of deionized water were added to the monomer and initiator feed vessels, respectively as rinses. The reaction was held for 20 minutes at 91°C. The resulting theoretical end of feed solid was 51.2%.
  • a chase promoter solution of 4.5 grams of a 0.15% iron sulfate heptahydrate solution and 80 grams of deionized water was mixed and set aside.
  • the chaser solution of 0.5 grams of sodium persulfate dissolved in 5 grams of deionized water and adding 1.42 grams of 35% hydrogen peroxide, and set aside.
  • the promoter solution was added to the kettle and the persulfate / peroxide solution was added to the kettle over 5 minutes. The reaction was then held for another 30 minutes.
  • the following solution was prepared: a scavenger solution of 11.4 grams of sodium metabisulfite dissolved in 32 grams of deionized water.
  • Example #4 (Weight % Composition: 60% Acrylic Acid /40% Maleic Acid)
  • the example #5 was repeated, with the following differences:
  • the initiator cofeed solution was prepared by dissolving 2.1 grams of sodium persulfate in 20 grams of deionized water and 25.4 grams of 35% hydrogen peroxide was added and mixed, then added to a syringe for addition to the kettle.
  • the theoretical end of feed solid was 51.1%. (The measured end of feeds solids was 52.5%).
  • An initiator solution of 2.1 grams of sodium persulfate dissolved in 20 grams of deionized water was mixed and 9.13 grams of 35% hydrogen peroxide was added to the sodium persulfate solution, mixed well and added to a syringe for addition to the kettle.
  • a monomer pre-charge solution of 19.26 (0.267 moles) grams of glacial acrylic acid was placed in a vial and set aside.
  • An initiator pre-charge solution was prepared by dissolving 1.48 grams of sodium persulfate dissolved in 8 grams of deionized water and adding 2.93 grams of 35% hydrogen peroxide, and set aside.
  • a promoter solution of 4.5 grams of a 0.15% iron sulfate heptahydrate solution was added to a vial and set aside.
  • the promoter solution was added, followed by the acrylic acid pre-charge. After 1 minute, the initiator pre-charge solution was added to the kettle. The expected exotherm of 2 - 5 °C was observed within 5 minutes. One minute after peak exotherm, the monomer and initiator cofeeds began and added linearly and separately over 120 minutes at 91-93°C. At the completion of the feeds, 12 grams and 4 grams of deionized water were added to the monomer and initiator feed vessels, respectively as rinses. The reaction was held for 20 minutes at 91 °C. The resulting theoretical end of feed solid was 54.6%.
  • a chase promoter solution of 9.0 grams of a 0.15% iron sulfate heptahydrate solution and 80 grams of deionized water was mixed and set aside.
  • the chaser solution of 0.5 grams of sodium persulfate dissolved in 5 grams of deionized water and adding 1.42 grams of 35% hydrogen peroxide, and set aside.
  • the promoter solution was added to the kettle and the persulfate / peroxide solution was added to the kettle over 5 minutes. The reaction was then held for another 30 minutes.
  • the following solution was prepared: a scavenger solution of 11.4 grams of sodium metabisulfite dissolved in 32 grams of deionized water.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (6)

  1. Ein Verfahren zur Herstellung von aliphatischen Dicarbonsäure-Copolymeren mit hohem Molekulargewicht, das Folgendes beinhaltet:
    i) Bereitstellen mindestens eines Dicarbonsäure-Monomers;
    ii) Bereitstellen mindestens eines α,β-ethylenisch ungesättigten Monomers, ausgewählt aus der Gruppe, die aus Folgendem besteht:
    (a) einer Monocarbonsäure mit 3 bis 10 Kohlenstoffatomen und den Alkalimetall- und Ammoniumsalzen davon;
    (b) einer organischen Sulfonsäureverbindung und den Alkalimetall- und Ammoniumsalzen davon;
    (c) einem Vinylmonomer, das frei von Carbon- und Sulfonsäuregruppen ist; und
    (d) Mischungen aus (a), (b) und (c);
    iii) Bereitstellen mindestens eines Übergangsmetallions, ausgewählt aus der Gruppe, bestehend aus Zn2+, Co3+, Co2+, Cu2+, Mo2+, Fe3+, Fe2+, Cr3+, Ni2+, Ce4+ und Ce2+, und Mischungen daraus, in einer Konzentration von von 0,5 bis 100 ppm basierend auf dem gesamten wässrigen Polymerisationssystem einschließlich Monomere und Initiator;
    iv) Einspeisen der mindestens einen Dicarbonsäure, des mindestens einen α,β-ethylenisch ungesättigten Monomers und eines Initiators in ein Reaktionsgefäß, wobei der pH in dem Reaktionsgefäß von 9,5 bis 7,5 reicht
    v) Reagierenlassen der mindestens einen Dicarbonsäure, des mindestens einen α,β-ethylenisch ungesättigten Monomers und Initiators; und
    vi) Produzieren eines Copolymers aus aliphatischen Dicarbonsäuren, mit einem berechneten Endeinspeisungsfeststoffgehalt, der von 46 bis 60 % reicht, und einem Gewichtsmittel des Molekulargewichts von 70000 bis 180000 Dalton, wie durch Gel-Permeations-Chromatographie (GPC) unter Verwendung von Polyacrylsäure-Standards gemessen, und einem von 4000 bis 0 ppm reichenden Restgehalt, wobei der Restgehalt die Gesamtgewichtsmenge von unreagierter Dicarbonsäure geteilt durch das Gesamtgewicht der Reaktionsmischung ausgedrückt in Teilen pro Million ist.
  2. Verfahren gemäß Anspruch 1, in wobei die mindestens eine Dicarbonsäure, das mindestens eine α,β-ethylenisch ungesättigte Monomer und ein Initiator über einen Zeitraum von weniger als oder gleich 3 Stunden eingespeist werden.
  3. Verfahren gemäß Anspruch 1, wobei der pH bei Ende der Einspeisung der mindestens einen Dicarbonsäure, des mindestens einen α,β-ethylenisch ungesättigten Monomers und eines Initiators von 4 bis 5,5 reicht.
  4. Verfahren gemäß Anspruch 1, wobei der Initiator aus der Gruppe ausgewählt ist, die aus Wasserstoffperoxid, t-Butylhydroperoxid, Natriumpersulfat, Kaliumpersulfat, Ammoniumpersulfat und 2,21-Azobis(2-amidinopropan)hydrochlorid besteht, und in einer Menge von von 0,5 bis 5 Gewichtsprozent der gesamten Monomere vorhanden ist.
  5. Verfahren gemäß Anspruch 1, wobei das Dicarbonsäure-Monomer Maleinsäure, ein Monoalkalimetallmaleat oder ein Monoammoniummaleat ist.
  6. Verfahren gemäß Anspruch 1, wobei von 0,5 bis 10 ppm des Übergangsmetallions vorhanden sind.
EP10152291A 2009-02-18 2010-02-01 Verfahren zur Herstellung von verbesserten aliphatischen Dicarboxylsäure-Copolymeren Active EP2221324B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US20797509P 2009-02-18 2009-02-18

Publications (2)

Publication Number Publication Date
EP2221324A1 EP2221324A1 (de) 2010-08-25
EP2221324B1 true EP2221324B1 (de) 2013-01-16

Family

ID=42135961

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10152291A Active EP2221324B1 (de) 2009-02-18 2010-02-01 Verfahren zur Herstellung von verbesserten aliphatischen Dicarboxylsäure-Copolymeren

Country Status (4)

Country Link
US (1) US20100210802A1 (de)
EP (1) EP2221324B1 (de)
CN (1) CN101805418B (de)
CA (1) CA2691696C (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9574100B2 (en) * 2011-06-22 2017-02-21 Basf Se Coated polymer foils with oxygen barrier properties
CN103450860A (zh) * 2012-06-01 2013-12-18 天津中油渤星工程科技有限公司 一种改善水泥浆与钻井液相容性的分散剂
US9145340B2 (en) 2012-08-13 2015-09-29 Verdesian Life Sciences, Llc Method of reducing atmospheric ammonia in livestock and poultry containment facilities
US9961922B2 (en) 2012-10-15 2018-05-08 Verdesian Life Sciences, Llc Animal feed and/or water amendments for lowering ammonia concentrations in animal excrement
ES2744403T3 (es) * 2013-03-15 2020-02-25 Lubrizol Advanced Mat Inc Copolímeros de ácido itacónico
US11254620B2 (en) 2013-08-05 2022-02-22 Verdesian Life Sciences U.S., Llc Micronutrient-enhanced polymeric seed coatings
TW201522390A (zh) 2013-08-27 2015-06-16 特級肥料產品公司 聚陰離子聚合物
CA2923561C (en) 2013-09-05 2022-05-03 Verdesian Life Sciences, Llc Polymer-boric acid compositions
CA2945823C (en) 2014-05-21 2022-04-26 Verdesian Life Sciences, Llc Polymer soil treatment compositions including humic acids
CA2946202C (en) 2014-05-22 2022-06-21 Verdesian Life Sciences, Llc Polymeric compositions

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57168906A (en) * 1981-04-13 1982-10-18 Kao Corp Maleic acid/(meth)acrylic acid copolymer
US5175361A (en) * 1981-09-28 1992-12-29 Basf Aktiengesellschaft Preparation of copolymers of monoethylenically unsaturated monocarboxylic acids and dicarboxylic acids
DE3233778A1 (de) * 1982-09-11 1984-03-15 Basf Ag, 6700 Ludwigshafen Verfahren einer kontinuierlichen herstellung von copolymerisaten aus monoethylenisch ungesaettigten mono- und dicarbonsaeuren
US4659793A (en) 1986-03-03 1987-04-21 Alco Chemical Corporation Preparation of aqueous solutions of copolymers of dicarboxylic acids having a low dicarboxylic acid monomer content
US5055540A (en) * 1990-02-06 1991-10-08 Rohm And Haas Company Process for efficient molecular weight control in copolymerization
US5451644A (en) * 1994-01-14 1995-09-19 Rohm And Haas Company Aqueous process for preparing water soluble polymers of monoethylenically unsaturated dicarboxylic acids
US6444771B1 (en) * 1998-09-08 2002-09-03 Nippon Shokubai Co. Ltd. Acrylic acid-maleic acid copolymer (or its salt), its production process and use, and production process for aqueous maleic salt solution with low impurity content
EP1308944A3 (de) * 2001-10-30 2007-10-17 Sony Corporation Verfahrun zur Herstellung eines Informationsaufzeichnungsmediums, Herstellungsvorrichtung und Informationsaufzeichnungsmedium
JP2007052863A (ja) * 2005-08-18 2007-03-01 Toshiba Corp 光ディスク、光ディスク作製方法、光ディスク装置
JP2008059702A (ja) * 2006-08-31 2008-03-13 Toshiba Corp 光ディスク及びこの光ディスクを用いた光ディスク装置

Also Published As

Publication number Publication date
CN101805418B (zh) 2013-11-27
EP2221324A1 (de) 2010-08-25
CA2691696A1 (en) 2010-08-18
CA2691696C (en) 2013-07-09
US20100210802A1 (en) 2010-08-19
CN101805418A (zh) 2010-08-18

Similar Documents

Publication Publication Date Title
EP2221324B1 (de) Verfahren zur Herstellung von verbesserten aliphatischen Dicarboxylsäure-Copolymeren
EP0236103B1 (de) Herstellung wässriger Lösungen von Copolymeren von Dicarbonsäuren mit niedrigem Gehalt an Dicarbonsäuremonomeren
US5256746A (en) Low molecular weight monoalkyl substituted phosphinate and phosphonate copolymers
KR100309221B1 (ko) 하이포포스포러스산혹은그염을사슬전달제로사용한에틸렌계불포화단량체로부터유도된중합체제조방법
EP3078650B1 (de) Mit polyanionischen polymer umhüllte samen enthaltender samenprodukt
EP0441022B1 (de) Wasserlösliche Copolymere mit niedrigem Molekulargewicht, Verfahren zu deren Herstellung und diese enthaltende Wasch- und Reinigungsmittel
KR20110081324A (ko) 수성 매질내에서 부식을 억제하기 위한 조성물 및 방법
US20020115798A1 (en) Star-branched anionic polymers
JP6504177B2 (ja) アクリル酸系共重合体の製造方法
JP2011072851A (ja) アミノ基含有共重合体を含むスケール防止剤
CN110066028B (zh) 无磷缓蚀阻垢剂组合物和无磷缓蚀阻垢剂及其应用
JP2771864B2 (ja) マレイン酸系共重合体の製造方法
CA2840781C (en) Preparing maleic acid-isoprenol copolymers
CN111718443B (zh) 无规共聚物及其制备方法、应用以及钻井液
CN110066032B (zh) 低磷缓蚀阻垢剂组合物和低磷缓蚀阻垢剂及其应用
JPH0146594B2 (de)
CN110066027B (zh) 无磷缓蚀阻垢剂组合物和无磷缓蚀阻垢剂及其应用
US20130180926A1 (en) Preparing maleic acid-isoprenol copolymers
CN110066033B (zh) 低磷缓蚀阻垢剂组合物和低磷缓蚀阻垢剂及其应用
KR20150014046A (ko) 폴리카르복실산계 공중합체 및 층상형 이중 수산화물을 포함하는 시멘트 혼화제 및 이의 제조 방법
JPH0762263B2 (ja) 金属の腐蝕抑制剤の製造方法
JPH0141706B2 (de)
JPS5950399B2 (ja) スケ−ル防止剤
JPH05169092A (ja) 水系処理剤の製造方法
JPS6247600B2 (de)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20100201

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

AX Request for extension of the european patent

Extension state: AL BA RS

17Q First examination report despatched

Effective date: 20100902

RIC1 Information provided on ipc code assigned before grant

Ipc: C08F 222/06 20060101ALI20120725BHEP

Ipc: C11D 3/37 20060101ALI20120725BHEP

Ipc: C08F 220/04 20060101ALI20120725BHEP

Ipc: C08F 220/06 20060101AFI20120725BHEP

GRAC Information related to communication of intention to grant a patent modified

Free format text: ORIGINAL CODE: EPIDOSCIGR1

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 593885

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130215

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602010004574

Country of ref document: DE

Effective date: 20130314

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 593885

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130116

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20130116

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130516

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130427

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130416

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130416

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130417

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130516

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

26N No opposition filed

Effective date: 20131017

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130201

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602010004574

Country of ref document: DE

Effective date: 20131017

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140228

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20100201

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130201

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130116

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230525

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231214

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20231212

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231205

Year of fee payment: 15